Tetrakisazo dyes



Patented Aug. ll, 1%25.

JAMES P. yENNY, F BUFFALO. NEW YORK, ASSIGNOR Tl") NATIONAL AIHLIN'ECHEMICAL 00., ING. OF NEW] YORK, N. Y., A CORPORATION OF YORK.

TE'I'RAKISAZO DYEE.

E le Drawing.

To all whom it may concern:

Be it known that I. JAuns P. PENNY, a citizen of the United States,residing art Butfulo. in the county of Erie, State of New u York, haveinvented certain new and useful liuprovements in 'lttrukisnzo Dyes; andl do hereby declare the following to be a full, clear, and exactdescription of the inven tion, such as will enable others skilled in inthe art to which it appertains to make and use the same.

This invention relates to the manufacture and production of valuable newtetrakisazo dyes which are particularly suitable for dyeltl ing cottonand other vegetable fibers from neutral or an alkaline bath. Materialsdyed with the new dyestufis also form a part of the present invention.

The new tetrakisezo dyes of the present invention can be obtained bydiazotizing and coupling two molecular proportions of the sametlllllllUdZO compound, or by coupling one molecular proportion each oftwo dill'erent diazotized aminoazo compounds,

with one molecular proportion of 5.5 dil. a h

Application filed October 29, 1924. Serial No. 74.8,573.

hydroxy2.2'-dinephthylurea-7.7 -disulfonic ucid (i. e., the symmetricalurea of 2.5-aminonaphthol-T-sulfonic acid).

The aininoazo compounds concerned with and employed in the presentinvention comprisev those derivable from a beta-naphthylilllllIOCdisulfonic acid as first component and :1 primary amine of the benzeneseries having a free para position as second component, and theycorrespond in general to the following probable formula:

(Benin wherein R represents a hydrocarbon radical of the benzene seriesand :1: represents a hydrogen atom which may be replaced by an alkoxygroup such as, -0GH -OC H etc.

:lhe new tetrakisazo dyes are salts of an acid having most probably thefollowing general formula:

giving generally blue to green solutions; yielding upon reduction withstannous chloride and hydrochloric acid, a bete-napththylaininedisul'l'onic acid, a parwdiamiue of the benzene series und5.5-dihydroxy- 6.6 diamii1o--2.2- dinaphthylurea -7.7-disultonic acid;und dyeing cotton from an elk? line or neutral buth yellowish-red tobluishred tints or excellent tastncss to light which are capable ol'being discharged by the action of reducing agents, such as, for example.sodium hydrosnltite.

The following examples will further'illusrate the invention, butit isunderstood that the invention is not limited thereto. The parts are byWeight.

Example 1: 4-5.1 parts (2 mols) of the sodium salt of the aminoazocompound which can be obtained by coupling one molecular; proportion ofdiazotized 2-naphthylamine- 6.8-disulfonic acid with one molecularproportion of the N-methyhomega-sultonic acid derivative of aniline(that is, the formaldehyde-bisulfite compound of aniline,

and subsequently eliminating the N-methylomega sullonicacid group isdiazotized with (3.9 parts of sodium nitrite, 30 parts of hydrochloricacid, sp.'gr. 1.16, and 900 parts water at a temperature of about 0 to 5C. Ex-V cess of nitrous acid is avoided. To the resulting diazosolution, While being stirred and maintained at a temperature of aboutll "x and in the dried and pulverized state in the shape of its sodiumsalt is a grayish powder soluble in water giving a bluish-red solution,and soluble in concentrated sulfuric acid giving a greenish solutionwhich on the addition of ice produces a violet colored precipitate. Uponreduction with stannous chloride and hydrochloric acid it is decomposedand' yields :Z-aminonaphthalene-G.S

disulfonic acid, lzd-diaminobenzene, and

the symmetri cal urea of 2.6-diamino-5-naphtholJ-sulfonic acid. It dyescotton from a neutral or alkaline bath bluish-red tints which are ofexcellent fastness toward light and are capable of being discharged bythe action of sodium hydrosuliite.

Example 2: 45.1 (1 mol) parts of the sodium salt of the aminoazocompound which can be obtained by coupling diam-i tizedQ-naphthyiamine-fifidisulfonic acid{ with the formaldehyde-bisulfitecompound of aniline and subsequentlyeliminating theformaldehydebisulfite group are dissolved 0 to 5 (1, there is slowlyadded an ice-cold solution of 27 parts (1 mol) of the sodium. 1

.salt of 5.5-dihydroxy-2.2-dinaphthylureacommon salt, filtered off,pressed and dried.

The new dyestufi' thus obtained is the sodium salt of an acid having thefollow.- ing probable formula:

in 900 parts of water vcontaining 29.4 parts of hydrochloric acid; sp.gr. 1.1.6, and chazo tized at a temperature of about 0 to 5 C. witlrdf)parts sodiumih trite; The resulting diazo solution is then iiidded to asolution of 54.8 parts (1 mol) of tliesodium salt of the symmetricalurea vof 2.5-amino-naphthol-Z- sulfonic acid in 1000 parts watercontaining sufficient ice to maintain the temperature at about 0 to 50., and then slowly adding sodium acetate to the well stirred mixtureuntil a neutral reaction toward Congo red test paper is-obtained. Uponthe completion of the combinationthere is added to the so- 'lution ofthe disazo dye thus obtained a diazo solution prepared by diazotizing,with the aidiof 6.9 parts sodium nitrite, 29.4 parts of hydrochloricacid, sp. gr. 1.16, and 900 parts water,j49.'5 parts (1 mol) of thesodium salt'of the vaininoazo compound which can be obtained by'couplingdiazotized 2naphthylamine-6.8-disulfonic acid with cresidine. Suficientsodium carbonate is then added to rec-ems the mixture to render italkaline towerd brilliant yellow test paper. After being stirred at atemperature of to '5 C. for

several hours the formation of the dycstutf' will be complete. It isthen precipitated by the addition of common suit, filtered oil',

The dyestuil thus obtained dissolves in water giving a bluishredsolution vand in concentrated sulfuric acid giving a greenislrbluesolution; and yields upon reduction with stennous chloride andhydrochloric acid Q-naphthylamine- 6.8-clisulfonic acid,1.4-(llilmlIl0lJQl'lZOIlL, 3.6- diamino-4-methoxytoluene, and a snunetrical urea. of 2.6-diamino--napht1ol-7-sulfonic acid. It dyescotton Bordeaux hades from a neutral bath.

Other valuable new tetrakisazo d es are produced in an analogous mannerby employing other aminoazo compounds, for exam le, such as areobtainable from Q-naphthy amine-6.8-disulfonic acid,Q-naphthylam1ne-5-7-disulfonic acid, 2-nephthylemine 3.6-disulfonicacid, 2-na hthylemine-fidisulfonic acid, Q-Be h hylamine'LG-disuI- tonicacid, 2-naphthyl:uuine-ili-disnlionic acid, 2 naphthyluminc 4.7disulfonic :ic -l and other Q-uminonuphihulene disulfonie acids as firstcomponent on the one hand and aniline, oand m-loluidinc, xylidine, oandm unisidine, -l--metlr\ l-2-umino-l-methoxybenzene and other primaryamines of the benzene series having a tree pure position us secondcomponent on the other hand. lYhile the preparation of the mninouzocompounds can be.generallyeffected by the direct combination of thediazotized 2-nuphthylumine disulfonic acids with the primary amines ofthe benzene series having a free para position yet in some cases it isadvantageous to proceed by way of the frn'maldehydc-bisulfite compoundof the amine, for example,

when couplin into aniline, o-toluidine or 0- anisidine, an subsequentlyeliminating the formaldehyde-bisulfite group in any suitable way orwell-known manner.

I claim 1. As new products, tetrekisezo dyestuils having most probablythe formula:

(Son I beta-ncphthylamine disulfonic ec'id, psrediumine of the benzeneseries and 5.5'-dihydroxy 6.6-diamino-2.2-dinaphthyluree- T.7-disulfonicacid; and dyeing cotton yellowish-red to bluish-red tints which arecepubic of being discharged by the notion of reducing agents.

2. As new products, tetrekisezo dyestufi's having most probably theformulu:

25 hydrqchloric ac &

wherein R represents a hydrocarbon of the be 0110 series and a? anallu'xxy group such as: OCH ()(LH elm: said alyegtuii's in the shape oftheir sodium salts heing; pmwiers soluble in Water and in soncentrntcdsulfuric acid; yielding upi'iu reduction with stannous chloride and.hydrochloric acid :1 betanaphthylmnine disulfonic amine of the benzeneseries containing an wherein llrepresenits ii, hydrocarbon radical ofthe benzene series; said Ll vostulls in (he dry and pulverized siate inthe shape of their sodiurgi salts being? soluble in water and in contluliil sulfuric acid; yielding" upon reduction 1th stannous chlorideand. 0- i hatw-unphthylzunine climine. 0f I the benzene sulfonic acid,3/ li which in the dry uncl pulverizacl state in the shape of theirsodium szilas are grayish powders soluble in water with a bluish-red toa yellowishq'ecl coloration and soluble in concentmiieil sulfuric midwith a, blue to acid, a para-chseries containing 110 i'zllmxy group, andasyn'nuoiricul u T821 ml 26- (i1?! 1m n ofi-na ph- Y tholJ-sulfnmcflflhi; and dyeing cotton hlu' hrecl tints which are capable of. being30 discharged by the action of reducing agents."

14. As new products, fQtrakisazci dyestuffs having most probably the.fim'mula:

u- 1 l'x /l green coloration; yielding upon reductionv with si'iannouschloride, and hydrochlori qiqn acid a betwami onaphthiilene disulfonicacid, paira-pl'ie11y1ene(iigumx gg and a ym-f metrical urea of2.6-d1a1xfi1io-5-naphthoL7- mo em 7 sulfonic acid; and dyeing cottonbluish-red 5. As a new product, the tetrakisazo dyetints which arecapable of being discharged stufi having most probably the formula: 5 bythe action of reducing agents.

ll ill which in the dried and pulverized state and 6. Material dyed withthe dyesfaifisv of in the shape of its sodium salt is & grayish claim 1.20 powder soluble in Water giving bluish-fed 7 Material dyed with thedyestufi's of solution, and soluble in concentrated salclaim 2. W furioacid giving a greenish solution; yield- 8. Material dyed with thedyestuffs of iz lg upon reduction with stannous chloride claim 3. andhydrochloric acid 2-11apl1thylamine-6.8-

Materiel dyed with the dyestufl of 25 disulfonio acid,para-phenylenedlamihe and Ola-1m 4w u K 5.5-dihydroXy-6.6glhamino-QB-naphtl1ylaterial dyed wlth the dyestufl of urewZT-disulfonicacid; and dyeing cotton QlEQm bluish-red shades which are capable of bein testlmony whereof I a'ffix y a ing discharged by the action ofreducing a JAWS P. PENNY.

